The Relationship Between Redox-Sensitive Element Behaviors and Redox Conditions in Miocene Aged Bituminous Claystones of the Ilgın (Konya) Basin

Yıl 2024, Cilt: 14 Sayı: 2, 61 - 84, 23.07.2024

Ali Sarı , Kamal Ismayılzada , Sinan Akıska , Fuat Erol

Öz

In this study, the redox-sensitive trace elements in the Miocene-aged bituminous claystones rich in shallow organic matter (%TOC: 14.52-44.44; avg: 31.24) in the Ilgın basin (Konya) were investigated. The elements studied include Vanadium (V), Uranium (U), and Molybdenum (Mo), as well as Zinc (Zn), Nickel (Ni), Copper (Cu), and Cobalt (Co), aiming to analyze their geochemical behaviors. Additionally, the influence of the basin’s redox conditions on organic matter accumulation was examined. For this purpose, 14 samples were systematically collected from the bituminous claystones, starting from the lignite level at the base up to the top. In the investigation of the behavior of redox-sensitive elements in the Miocene-aged bituminous claystones in the Ilgın area, the relationships between major and trace elements and their total organic carbon (%TOC) content were examined. Major and trace element analyses were conducted on samples using an ICP-OES device, and %TOC analyses were performed using a Rock Eval VI device. In the examined bituminous rocks, there are moderate correlations between %TOC and %Mo (r=0.529); weak and very weak correlations are observed for Cu (r=-0.230), Ni (r=-0.030), Zn (r=0.216), U (r=0.083), V (r=0.124), and Co (r=0.076). This indicates that the enrichment of these elements in sediments and sapropels from water masses does not involve organometallic ligands in humic acids except for Mo. Very weak correlation relationships of Fe with U (r=0.204), Ni (r=0.029), and Zn (r=-0.142) indicate that the enrichment of U and Zn in sapropel is not influenced by pyrite. However, the moderate correlation of Fe with Co (r=0.535) and strong correlation with Mo (r=0.722) suggest that the enrichment of Co and Mo in sapropel is influenced by pyrite. Very weak correlations between Mn and Cu (r=-0.562), Zn (r=-0.163), Ni (r=-0.318), V (r=-0.243), U (r=-0.142), and Mo (r=-0.600) indicate that manganese oxyhydroxides play no role in the diffusion and enrichment of these elements from water masses to sapropel. Sulfur shows very weak correlations with Ni (r=-0.121), V (r=-0.177), and Zn (r=-0.354); weak correlations with Cu (r=0.290) and U (r=0.302); moderate correlation with Co (r=0.476); and strong correlation with Mo (r=0.729). This suggests that Co precipitates as CoS and Mo as MoS2, while Cu, Zn, Ni, U, and V do not enrich as sulfides. A very strong correlation (r=0.929) between Fe and S indicates that Fe precipitates as pyrite (FeS2), suggesting an anoxic redox condition. The redox conditions in the basin are oxic/suboxic and anoxic based on Th/U ratios in all samples, except for samples RE-1 and RE-7; based on U/Th ratios, except for samples RE-1 and RE-7; and based on V/V+Ni ratios, except for samples RE-1, 2, 3, 6, and 12.

Anahtar Kelimeler

Anoxic environment, bituminous claystone, element enrichment, redox condition, organic matter

Ilgın (Konya) Havzası Miyosen Yaşlı Bitümlü Kiltaşlarındaki Redoksa Duyarlı Element Davranışları ve Redoks Koşulları Arasındaki İlişki

Öz

Bu çalışmada, Ilgın (Konya) havzasında yüzlek veren organik maddece çok zengin (%TOC:14.52-44.44; ort:31.24) Miyosen yaşlı bitümlü kiltaşlarındaki redoksa duyarlı iz elementlerin: Vanadyum (V), Uranyum (U) ve Molibden (Mo), Çinko (Zn), Nikel (Ni), Bakır (Cu) ve Kobalt (Co) jeokimyasal davranışlarının incelenmesi ve havzanın redoks koşulunun organik madde birikimindeki etkisinin ortaya konulması amaçlanmıştır. Bu amaçla, tabandaki linyitli seviyesinden başlayarak tavana kadar sistematik olarak bitümlü kiltaşlarından 14 adet örnekleme yapılmıştır. Ilgın sahasındaki Miyosen yaşlı bitümlü kiltaşlarında redoksa duyarlı element davranışlarının incelenmesinde ana ve iz elementler ile bunların toplam organik madde (%TOC) ile olan ilişkileri incelenmiştir. Örneklerde ana ve iz element analizleri ICP-OES cihazında ve %TOC analizleri de Rock Eval VI cihazında yapılmıştır. İncelenen bitümlü kayaçlarda %TOC ile %Mo’nin (r=0.529) orta derecede; Cu (r= -0.230), Ni (r= -0.030), Zn (r= 0.216), U (r=0.083), V (r=0.124) ve Co’ın (r=0.076) çok zayıf ve zayıf korelasyonları bulunmaktadır. Bu durum, Mo dışındaki diğer elementlerin su kütlesinden sapropele difüzyonunda ve tortullarda zenginleşmelerinde hümik asitlerdeki organometalik ligandların etkisinin olmadığını gösterir. Fe’in U (r= 0.204), Ni (r= 0.029) ve Zn ile (r= -0.142) olan çok zayıf korelasyon ilişkileri, U ve Zn’nun sapropelde zenginleşmelerinde piritin etkisinin olmadığını gösterir. Ancak, Fe’in Co ile (r= 0.535) orta ve Mo ile de (r= 0.722) güçlü korelasyon ilişkisi Co ve Mo’nin sapropelde zenginleşmesinde piritin etkili olduğunu gösterir. Örneklerde, Mn ile Cu (r= -0.562), Zn (r= -0.163), Ni (r= -0.318), V (r= -0.243), U (r= -0.142) ve Mo (r= -0.600) arasındaki çok zayıf korelasyon ilişkisi bu elementlerin su kütlesinden Mn oksi-hidroksitler ile sapropele difüzyonunda ve zenginleşmelerinde Mn oksi-hidroksitlerin hiçbir rol oynamadığını göstermektedir. Kükürt’ün Ni (r= -0.121), V (r= -0.177) ve Zn (r= -0.354) ile çok zayıf; Cu (r= 0.290) ve U (r=0.302) ile zayıf; Co (r=0.476) ile orta ve Mo ile de (r=0.729) kuvvetli korelasyon ilişkisi vardır. Bu durum, Co’ın CoS şeklinde, Mo’nin ise MoS2 şeklinde çökeldiğini; Cu, Zn, Ni, U ve V elementlerinin ise sülfid şeklinde bir zenginleşmelerinin olamadığını göstermektedir. Örneklerde, Fe ve S arasındaki çok güçlü (r=0.929) korelasyon ilişki Fe’nin pirit (FeS2) fazında çökeldiğini ve redoks koşulunun da anoksik olduğunu gösterir. Havzadaki redoks şartları; Th/U oranlarına göre tüm örneklerde; U/Th oranlarına göre RE-1 ve RE-7 numaralı örnekler dışında; V/V+Ni oranlarına görede RE-1,2,3,6 ve 12 numaralı örnekler dışında disoksik/suboksik ve anaoksiktir.

Anahtar Kelimeler

Anoksik ortam, bitümlü kiltaşı, element zenginleşmesi, redoks koşulu, organik madde

Teşekkür

Yazarlar, bu makaleyi eğitim-öğretimindeki 90. yıl münasebetiyle (1934-2024) Ankara Üniversitesi Jeoloji Mühendisliği Bölümü’ne (Ankara Jeoloji) ithaf ederler. Bu çalışmada incelenen örneklerde ana ve iz element analizleri A.Ü. YEBİM Araştırma Merkezinde ICP-OES (Inductively Coupled Plasma - Optical Emission Spectrometry) model cihaz kullanılarak yapılmış olup kendilerine teşekkür ederiz.

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